Mineral oil composition



United States Patent its MINERAL 01L COR [POSITION Robert H. Jones,Irvington, N. Y., assignor to Esso Research and Engineering Company, acorporation of Delaware No Drawing. Application July 1, 1953, Serial No.365,527

16 Claims. (Cl. 252-325) The art of metallic detergents for lubricatingoil cornpositions adapted for use in internal combustion engines is wellknown to those versed in this field and has resulted in substantialimprovements in lubricants. These detergents are particularly useful inlubricating oil compositions which are employed in internal combustionengines used in the operation of automobiles, aircraft and similarvehicles, including diesel engines, to improve their operation byreventing or retarding corrosion, piston ring sticking, cylinder wear,and carbon and varnish formation. However, when metallic detergents areused in lubricating compositions where oil consumption is high andengine conditions are severe, such as in aircraft engines or where suchconcentrations of metallic detergents are used to maintain enginecleanliness under conditions Where high deposit fuels of cracked or highsulfur nature are used, such as in automobile and diesel operation, theash content from the metallic detergent accumulates in the combustionchamber and causes pre-ignition, detonation, spark plug fouling, valveburning, and ultimate destruction of the engine.

It has been found in accordance with the present invention, that if thereaction product of a phosphorus sulfide or a mixture of phosphorus andsulfur with an essentially hydrocarbon product is treated withsemicarbazide or thiosemicarbazide, or with any of the substitutionproducts or derivatives thereof as hereinafter defined, the product soformed is very stable at the temperatures of engine operation and servesthe purpose of a good detergent and antioxidant. When incorporated inmineral lubricating oil which is used in an internal combustion engine,and because it contains no metal, it is free from the objectionablefeature of leaving a metallic deposit or ash. These compounds areeffective not only when added directly to the crankcase lubricant butalso when added to the engine fuel, since in the operation of the engineit will work its Way from the combustion chamber into the crankcase andthere blend with the lubricant.

The mechanism whereby the phosphorus sulfide-hydrocarbon reactionproducts are improved by treatment with semicarbazide type compounds hasnot yet been completely worked out. It appears, however, thatneutralization or partial neutralization by the semicarbazide type baseof acidic groups present in the phosphorus sulfide treated hydrocarbonmay be at least partially involved. Applicant of course does not wish tobe limited by theories of mechanism.

semicarbazide and thiosemicarbazide and their derivatives may beemployed as reagents for treating the phosphorus sulfide-hydrocarbonreaction product. The free base is entirely suitable and is generallypreferred. However, the final products can be formed by double decom-2,759,892 Patented Aug. 21, 1956 position of an inorganic acid salt ofthe base with a metal salt of the phosphorus sulfide-hydrocarbonreaction product. For example, the hydrochloride or sulfate of the basecan be reacted with the sodium, calcium, barium, or other metallic saltof the phosphorus sulfide-hydrocarbon reaction product.

Preferably, the additive may be formed by preparing as a first reactionproduct (a) the products obtained by reacting a sulfide of phosphoruswith an essentially hydrocarbon material, (b) the products obtained byreacting a mixture of the elements of phosphorus and sulfur with anessentially hydrocarbon material or (c) the metal salts of (a) and (b),and then reacting the first reaction product with (d) a free basesemicarbazide-type compound as described below or (e) an inorganic saltof (d), provided that reaction products (a) and (b) are reacted onlywith compound (d) and reaction product (0) is reacted only withinorganic acid salt (2).

Broadly, the semicarbazide or thiosemicarbazide type basic compoundswhich may be reacted in accordance with the present invention may bedefined by the formula R1 R; X R4 ML JLN Rn s in which R1, R2, R3, R4,and R5 are each hydrogen or hydrocarbon groups containing 1 to 20 carbonatoms each, e. g., straight chain alkyl groups, such as methyl, ethyl,propyl, butyl, and higher straight and branched chain alkyl groups, suchas octyl, isooctyl, Z-ethylhexyl, decyl, dodecyl, tetradecyl, cetyl andstearyl radicals, and may also represent cycloalkyl, aryalkyl, aryl oralkylaryl groups, e. g., methylcyclohexyl, phenylethyl, phenyl, cresyl,and tert.-butylphenyl groups. It will be understood that R1, R2, etc.,may represent the same or different atoms or groups in the samemolecule. X in the formula represents oxygen or sulfur.

For the purpose of listing a number of representative examples ofderivatives of semicarbazide and thiosemicarbazide which areparticularly useful in accordance with the present invention, thepositions in the basic semicarbazide molecule may be indicated thus:

0(5) HzN-NH-HI-NH:

Representative basic materials are the following:

4-methyl thiosemicarbazide 4-ethyl thiosemicarbazide 4-phenylthiosemicarbazide 2-methyl-4-phenyl thiosemicarbazide 2-ethyl-4-phenylthiosemicarbazide 1,2-dimethyl-4-pheny1 thiosemicarbazide l-ethylsemicarbazide 2-propy1 semicarbazide 4-phenyl semicarbazide The sulfideof phosphorus which is employed in the reaction With the hydrocarbonmaterial can be P283, P255, P483, P457, or other phosphorus sulfide, ormixtures thereof, and is preferably phosphorus pentasulfide, P285.Mixtures of elemental phosphorus and sulfur can be employed, in whichcase it is preferable to employ white phosphorus and powdered sulfur.

The essentially hydrocarbon material which may be reacted with aphosphorus sulfide in the first step of the production of additives ofthe present invention may be parafiins, olefins or olefin polymers,diolefins, acetylenes, aromatics or alkyl aromatics, cyclic aliphatics,petroleum fractions, such as lubricating oil fractions, petrolatums,waxes, cracked cycle stocks, or condensation products of petroleumfractions, solvent extracts of petroleum fractions, 'etc., andderivatives of such hydrocarbon prodnets-containing small amounts ofadded elements, such as halogen or sulfur.

Essentially paraffinic hydrocarbons such as bright stock residuums,lubricating ''oil distillates, petrolatums or para'flin waxes maybe'employed. Of this class 'of compounds, bright stocks are highlypreferred. There may also be employed products obtained by condensingany of the foregoing hydrocarbons, usually through 'first halogenatingthe hydrocarbon, with aromatic shydrocarbons in the presence ofanhydrous inorganic halides, such as aluminum'chloride, zinc chloride,boron fluoride, and the like.

As-examplesof monoolefinsmay bementioned isobutylene, acrolein, decene,dodecene, cetene (C16), 'octadecene (C18), cerotene (C26), melene(Cso'), olefinic extracts from gasoline or gasoline itself,-crackedeycle'stocks and polymers thereof, resin oils fromcrude oil, hydrocarboncoal resins, cracked waxes, dehydrohalogenated chlorinated waxes, andany mixed high molecular weight alkenes obtained by cracking petroleumoils. A preferred class of olefins are those having at least20 carbonatoms per'molecule, of which from about 12 to about 18 carbon-atoms, andpreferably at least 15 carbonatoms, are in -'a long chain. Such olefinsmay be obtained by the dehydrogenation of paraffin waxes, by thedehydrohalogenation of long chain alkyl halides, by the synthesis ofhydrocarbons from C and H2, by the dehydration of alcohols, etc.

Another class of suitable olefinic materials .are the monoolefinpolymers, in which the molecular weight ranges from 100 to 50,000,preferably fromabout 250 to about 10,000. These polymers may be obtainedby the polymerization .of low molecular weight monoolefinichydrocarbons, such as ethylene, propylene, butylene, isobutylene, normaland isoamylenes, or hexenes, .or by the copolymerization of anycombination of the above monoolefinic zmaterials.

Diolefins which may be employed include well known materials such asbutadiene, isoprene, chloroprene, cyclopentadiene,2,3-dimethylbutadiene, pentadiene-1,3,-hexadiene-.2,4, terpenes andthelike. Acetylene and substitutedacetylenesmay similarly be employed.

Another class of unsaturated hydrocarbon materials which 'may beadvantageously employed in the preparation of the additives ofthisirivention are high molecular weight copolymers of lowmolecularweight monoolefins and diolefins. The copolymeriis prepared bycontrolled copolymerization of a low molecular weight olefin and anon-aromatic hydrocarbon showing the general formula CnH2n-a:, in whichat is 2 or a multiple of 2,'in the presence of a catalyst of the.Friedel-Crafts or peroxide type. The low molecular weight olefin ispreferably :an isoolefin or a tertiary base olefin preferablyv'onehaving less than 7 carbon atoms per molecule. Examples of such olefinsare isobutylene, 'Z-methylbutene-l,2eethylbutene-l, secondary andtertiarylbase an1ylene,.hexylenes, and the like. Examples of thenon-aromatic;hydrocarbons of the above formula which canbe used are.theconjugated diolefins listed in the preceding paragraph, diolefinssuch as 1,4-hexadiene, in whichthe double bond is not conjugated, aswell as the acetylenes. The copolymerization is preferably carried outinthepresenceof aluminumchloride, boron fluoride, or benzoyl peroxide,and the copolymer ispreferably one having a molecular weightof about1,000 to30,000.

Another class of essentially hydrocarbon materials whichmay likewise beemployed in the preparation of the additives of this inventionaresulfurized hydrocarbons, which may be prepared by reactinganyof theunsaturated hydrocarbons describedvabove with elemental sulfur, or byreacting such hydrocarbons with.a sulfur halide,.followed, if desired,by a dehydrohalogenation step, whichmay, for example, be accomplishedbytreating. the :sulfurized and halogenated hydrocarbon ,product withphenol or other aromatic hydrocarbon, or by heating the sulfurized andhalogenated hydrocarbon in the presence of a secondary or tertiarysaturated monohydric aliphatic alcohol of 4 to 16 carbon atoms at atemperature of IUD-320 F.

Another class of hydrocarbons which may be employed in a similar mannerare aromatic hydrocarbons, such as benzene, naphthalene, anthracene,toluene, xylene, diphenyl, and the like, as well as aromatichydrocarbons having alkyl substituents and aliphatic hydrocarbonshavingaryl substituents.

A still further class of hydrocarbons which may be employed in thereaction with sulfides of phosphorus are condensation products ofhalogenated aliphatic hydrocarbons with an aromatic compound, producedby condensation in the presence of aluminum chloride or otherFriedel-Crafts type catalyst. The halogenated aliphatic hydrocarbon ispreferably a halogenated long chain paraffinhydrocarbon having more than8 carbon atoms, such as parahin wav, petrolatum, oxocerite wax,- etc.High viscosity parafiin oils, particularly heavy residual oil which hasbeen treated with chemicals or-extracted with propane or other solventsfor the removal of asphalts, may be employed. The aromatic constituentmay be naphthalene, fluorene, phenanthrene, anthracene, coal tarresidues, .and the kile.

.Another type of hydrocarbon material which may be similarly employed isa resin-like oil which has a molecular weight of from about 1,000 to2,000 or higher, obtained preferably from a parafiinic oil which hasbeen dewaxed and which is then treated with a liquified normallygaseoushydrocarbon, e. g., propane, to precipitate a heavypropane-insoluble fraction. The latter isa substantially wax-free andasphalt-free product having 'a Saybolt viscosity at 210 F. of about1,000 to about 4,000 seconds or more.

The phosphorus sulfide-hydrocarbon reaction product may be readilyobtained byvreacting the phosphorus sulfide or mixture of elementalphosphorus and sulfur with one or more of the herein describedhydrocarbons at a temperature of about 200 F. to about 600 F., andpreferably from about 300 F. to about 550 F., using in the reactionmixture preferably from about one to'about three molecular proportionsof hydrocarbon to one atomicproportion of phosphorus and at leastone-third atomic proportion of sulfur in the sulfide of phosphorus ormixture of phosphorus and sulfur. Itis advantageous to maintain anonoxidizing atmosphere, such as an :atmosphere ofnitrogen, above thereaction mixture. Usually it is desirable to use an amount of thephosphorus sulfide that will completely react withthe hydrocarbon sothat no further purification becomes necessary. In thecase of thereaction of monoolefin polymers with P255 the .preferred ratio is onemolecular proportionof the sulfide of phosphorus to two to fivemolecular proportions of polymer. .In such case the reactionis:-continned until all or substantially all of the phosphorus sulfidehas reacted. The reaction time-is not critical, and the time required tocause'the maximum amount of phosphorussulfide to react will vary greatlywith the temperature. A reaction time of 2 to 10 hours is-freguentlynecessary. If desired, the reaction productzmay be further treated byblowing with steam, alcohol, ammonia, orzan amine atvan elevatedtemperature of-about 200 .F. to about 600 F. to improve theodor thereof.

,The additives of the present inventionmay then be prepared by reactingthe above phosphorus sulfide-hydrocarbonreaction product with theorganic basic compound. of the typedescribed herein, i. e.,semicarbazide, thiosemicarbazide, or salts or derivatives of the same.This reaction may be carried out, preferably ma nonoxidizing atmosphere,by contacting the phosphorus. sultide-hydrocarbonv reaction product,either as-such or. dissolved in a suitable solvent such as naphtha, withthe semicarbazide compound at a temperature of 35-500 F., morepreferably at a temperature of 200350 F. It has been found that somewhatsuperior products are formed when a water-soluble basic compound, e. g.,thiosemicarbazide, is dissolved in or mixed with water when contactedwith the phosphorus sulfide-hydrocarbon reaction product. It ispreferable to employ about onehalf to one mol of semicarbazide compoundfor each mol of hydrocarbon originally reacted with the phosphorussulfide or mixture of phosphorus and sulfur.

Since the additives of the present invention are to be dissolved inmineral oils, the hydrocarbons which are reacted with a sulfide orphosphorus and the semicarbazide compounds will be chosen with a view toprovide a product which is soluble in the oil base or which has marginalsolubility that it can be plasticized with a high molecular weightalcohol, ester, or other plasticizer.

When additives of the present invention are employed in minerallubricating oils, they are preferably added in proportions of about0.001 to about 10.0% and preferably 1.0 to about 6.0%. The proportionsgiving the best results will vary somewhat according to the nature ofthe additive and the specific purpose which the lubricant is to serve ina given case. For commercial purposes, it is convenient to prepareconcentrated oil solutions in which the amount of additive in thecomposition ranges from 25% to 50% by weight, and to transport and storethem in such form. In preparing a 1nbricating oil composition for use asa crankcase lubricant the additive concentrate is merely blended withthe base oil in the required amount.

In certain cases it may be found that the effect of adding compounds ofthe type described above to a lu-. bricating oil will be to increase thedetergent eifect of the oil without sufliciently providing oxidationresisting characteristics. In such a case it is advantageous to add tothe lubricant, in addition to the additives of the present invention, asubstance containing sulfur and/ or phosphorus. Elemental sulfur may beused for this purpose or an organic sulfur compound, particularly anorganic sulfur compound capable of being decomposed to give free sulfurat a temperature to which the lubricant is subjected during use.Examples of such organic sulfur compounds are sulfurized mineral oils,terpenes, olefins, and diolefins, sulfurized animal and vegetable oils,sulfurized isobutylene polymer, etc.

Below are given detailed descriptions of preparations of two examples oflubricating oil additives of the type described above as well as enginetests in which oils containing the additives were employed as thelubricant. It is to be understood that the examples are given asillustrations of the present invention and are not to be construed aslimiting the scope thereof in any way.

Example 1 (a) 1200 grams of polyisobutylene of a molecular Weight ofabout 1200 was placed in a 3-liter, 3-necked round bottom flask andheated to 300 F. 125 grams of phosphorus pentasulfide was added and thetemperature raised to 400 F. over a two-hour period, and heating wascontinued at this temperature for 3 more hours with stirring. Themixture was blown with nitrogen for another 5 hours at 400 F. and thenfiltered. 200 grams of the phosphorus pentasulfide-treatedpolyisobutylene thus prepared was dissolved in 200 grams of a solventextracted Mid-Continent distillate oil of 150 seconds (Saybolt) at 100F., thus forming an approximately 50% oil concentrate of the phosphoruspentasulfidepolyisobutylene reaction product.

(b) A slurry of about 5% by weight of free semicarbazide, based on theactive ingredient of the product of (a), was prepared by adding 18.0grams of sermcarbazide hydrochloride to a solution of 9.1 grams ofpotassium hydroxide in ml. of distilled water, and

adding this mixture to 250 grams of the phosphorus pentasulfide-treatedpolyisobutylene of (a) at 150 F.

The temperature was then raised over a 3 /2 hour period to 310 F., thereaction being conducted with vigorous stirring and a steady stream ofnitrogen was bubbled through the mixture during the entire heatingperiod.- The product was filtered to provide the finished additive.

Example 2 A 200 gram portion of a 50% concentrate of phos-' phoruspentasulfide-polyisobutylene reaction product, prepared as in Example1(a), was treated with 5 grams of powdered thiosemicarbazide at 300 F.for 3 hours and filtered to obtain the final additive.

Example 3.-Laus0n engine tests The additives prepared by the methods ofExamples 1 and 2 were each blended in a lubricating oil baseconsistsisting of a solvent extracted Coastal naphthenic oil of 60seconds (Saybolt) viscosity at 210 F. The blends contained 4% by weightof the concentrates or 2% by weight of active ingredients. The blendswere submitted to a standard Lauson engine test which was conducted byoperating the Lauson engine at 1800 R. P. M. for 20 hours with a 1.5indicated kilowatt load, 300 F. oil temperature, and 295 F. jackettemperature, using in each test one of the prepared blends as thecrankcase lubricant. A similar test was applied to the unblended baseoil. The oils were rated by a demerit system, wherein a perfectly cleansurface is given a rating of 0, while a rating of 10 is given to theworst condition which could be ex pected by the deposition of varnish onthat surface. Observations were also made of the loss in weight of thecopper-lead bearing in each test. The results are shown in the followingtable:

Piston Varnish Demerit Cu-Pb Bearing Weight Loss (Gm./ Bearing)Lubricant Base oil Base oil product of Example 1 Base oil product ofExample 2 Example 4.Lab0ratory bearing corrosion test Blends wereprepared containing 0.25% by weight each of the active ingredients ofthe additives prepared as described in Examples 1 and 2, using as a baseoil a solvent extracted Mid-Continent parafiinic lubricating oil of SAE20 grade. Samples of these blends and a sample of the unblended base oilwere submitted to a laboratory test designed to measure theeffectiveness of the additive in inhibiting the corrosiveness of atypical mineral lubricating oil towards the surfaces of copper-leadbearings. The test was conducted as follows:

500 cc. of the oil was placed in a glass oxidation tube (13 inches longand 2% inches in diameter) fitted at the bottom with a ,41. inch airinlet tube perforated to facilitate air distribution. The oxidation tubewas then immersed in a heating bath so that the oil temperature wasmaintained at 325 F. during the test. Two quarter sections of automotivebearings of copper-lead alloy of known weight having a total area of 25'sq. cm. were attached to opposite sides of a stainless steel rod whichwas then immersed in the test oil and rotated at 600 R. P. M., thusproviding sufiicient agitation of the sample during the test. Air wasthen blown through the oil at the rate of 2 cu. ft. per hour. At the endof each four-hour period the bearings were removed, washed with naphthaand weighed to determine the amount of loss by corrosion. The bearingswere then repolished (to increase the severity of the test), reweighed,and then subjected to the test for additional four-hour periods in likemanner. The results are given in the following table as corrosion life,which indicates the number of hours required for the bearings to losemg. in weight, determined by interpolation of the data obtainedimthevarious periods.

Bearing. corrosion Oil: life. (hrs.)

Unblended. base oil 10 Base oil+additive of Example 1 28 Baseoil+additive of Example 2 32 Theproducts of the present invention may beemployed not only in ordinary hydrocarbon lubricating oils but also inthe heavy duty type of lubricating oils which have been compounded.withv such detergent type additives as metal soaps, metal petroleumsulfonates, metal phenates, metalalcoholates, metal alkyl phenolsulfides, metal organo' phosphates, thiophosphates, phosphitesandthiophosphites, metal salicylates, metal xanthates and thioxanthates,metal thiocarbamates, amines and amine derivatives, reaction products ofmetal. phenates and sulfur, reaction products of metal phenates andphosphorus sulfides, metal phenol sulfonates and the like. Thus theadditives of the present invention may be used in lubricating oilscontaining such other addition agents as barium tert.-octylphenolsulfide, calcium tert.-amylphenol sulfide, nickel oleate, bariumoctadecylate, calcium phenyl stearate, zinc diisopropyl salicylate,aluminum naphthenate, calcium cetyl phosphate, bariumdi-tert.-amylphenol sulfide, calcium petroleum sulfonate, zinc, methylcyclohexyl thiophosphate, calcium dichlorostearate, etc. Other types ofadditives such as phenols and phenol sulfides may be employed.

The lubricating oil base stocks used in the compositions ofthisinvention may be straight mineral lubricating oils or distillatesderived from parafiinic, naphthenic, asphaltic, or mixed base crudes,or, if desired, various blended oilsmay be employed as well asresiduals, particularly those from which asphaltic constituents havebeen carefully removed. The'oils may be refined by conventional methodsusing acid, alkali and/0r clay or other agents such as aluminumchloride, or they may be extracted oils produced, for example, bysolvent extraction with solvents of the type of phenol, sulfur. dioxide,furfural, dichlorodiethyl ether, nitrobenzene, crotonaldehyde, etc.Hydrogenated oils, white oils, or shale oil may be em ployed as well assynthetic oils, such as esters and.polyethers as well as those prepared,for example, by the polymerization of olefins or by the" reaction ofoxides of carbon with hydrogen or-by the hydrogenationofcoal or itsproducts. Also, for-special applications, animal, vegetable or fish oilsor'their'hydrogenated; or voltolized products may be employedinadmixture with mineral oils.

For'the best resultsthebase stock chosen should .normally be that oilwhichwithout the new-additive present gives the optimum performance intheservice content: plated. However, sincesoneadvantage of the additivesis that their use also makesfeasiblethe employment of less satisfactorymineraloils or other oils, no, strict rule can be laiddown for; thechoice of the base stock. Certain essentials must of coursebe observed.The oil must possess the viscosity and volatility characteristics knownto be required for theservice contemplated. The'oil must be asatisfactory solvent for the additive, although in some cases auxiliarysolvent agents may be used. The lubricating oils, however: they may havebeen produced, may vary considerably inviscosity and other propertiesdepending upon the particular use for which they are desired, buttheyusually range from about 40 to 150 seconds (Sayboltlviscosity at"210F.. For the lubrication of certain lowand medium speed Dieselengines thegeneral practicehas often been to use a lubricating. oil base stockprepared fromnnaphthenic or aromatic crudes and having asaybolt'viscosity at 210 F. of 45. to 90 seconds and a viscosity indexof 0 to 50. However, in certain types of Diesel engine and-othergasolineengine service; oils of higher voscosity index 'are'oftenpreferred,

for example, up to 75 to 100, or even higher, viscosity index.

Intaddition to.the.;materials to beaddedaccordingto thepresentinvention, other agents may also be usedsuch as dyes, pour depressors,heat thickened fatty oils, sulfurized fatty oils, organo-metalliccompounds, metallicor other soaps, sludge dispersers, antioxidants,thickeners, viscosity index improvers, oiliness agents, resins, rubber,olefin polymers, voltolized fats, voltalized mineral oils, and/orvoltolized. waxes and colloidal solids such as graphitezor zinc. oxide,etc. Solvents and assisting agents, such as esters, ketone, alcohols,aldehydes, halogenated or nitratedcompounds, and thelike may also beemployed.

Assisting agentswhich are particularly desirable as plasticizers anddefoamers are the higher alcohols having 81 or. more carbon atoms andpreferably 8 to carbon atoms,.e. g., laurylalcohol, stearyl alcohol, waxoxidation alcohols, and the like.

In addition to being employed in lubricants the additivesiof the.present invention may also be usedin motor fuels, hydraulic fluids,torque converter fluids, cutting oils,.flushing oils, turbine. oils ortransformer oils, industrial'oils, process oils and generally asantixoidants or detergents in mineral oil products. They may also beused. in gear. lubricants and greases. Since they are powerful surface.active. agents,.they have practical use in dry cleaning-fluids, mineral,spirit and aqueous paints, in flotation agents, and. as dispersants forinsecticides in aqueous'andtnoneaqueous solutions and for carbon blackin rubber: mixes;

What is claimed is:

1. A mineraloil containing a detergent quantity of a product obtained:bypreparing a first reaction product chosen from the. group consisting:of(a) the products obtained by reacting a sulfide of phosphorus with anessentiallyhydrocarbon material (b) the-products obtained by.reactingamixture of: the elements of phosphorus-and sulfur withan'essentially hydrocarbon material and (c) themetal salts of (a) and(b), and then by reacting.

the saidzfirst reactionproduct with an organic compoundselected'fromthegroups consisting of (d) compound of the composition,

wherein" R1, R2, R3, R4, and R5 are each selected. from the groupsconsisting of hydrogen and hydrocarbon radicals containing l toZOcarbonatoms each, and X- is selected from the group consistingsof'oxygen andsulfur and (e) an inorganic acid salt of (d) provided that reactionproducts-(a-) and (b) are reactedonly with com-. poundtd) and reactionproduct (c)'is reacted only with inorganic acid salt (e).

2. A composition according to claim 1 in which the mineral oil is'alubricating oil fraction.

3..A composition according to claim 1 in which said sulfideofphosphorusis phosphorus pentasulfide.

4. Acomposition according to claim 1 in which R1, R2, R 3, and R-.and.Rs.0f the formula each represent hydrogen.

5..A. compositionaccording to claim 2' in which X of the formularepresents oxygen.

6. A composition according to claim 2'in which R1, Rz,.R3, R andRs-ofthe formula each represent hydrogen.

7..A.composition.according to claim 2 in which R1, 112,113, R4 and R5 of.the formula each represent hydrogen and in which X of the formularepresents oxygen.

8. A compositionaccording. to claim 2in which said first reactionproduct is. the product obtained by reacting a phosphorus sulfide with ahydrocarbon material and in whiehsaidfirst reaction product is thenreacted with thiosemicarbazide;

.9. .A-composition according. ot claim 2 inwhich' the phosphorus sulfideis phosphorus pentasulfide and in which the hydrocarbon material whichis reacted with the same is a monoolefin.

10. A composition according to claim 2 in which the phosphorus sulfideis phosphorus pentasulfide and in which the hydrocarbon material whichis reacted with the same is a paraflinic lubricating oil bright stockfraction.

11. A mineral lubricating oil containing a detergent quantity of aproduct obtained by reacting phosphorus pentasulfide with a monoolefinpolymer and reacting such reaction product with thiosemicarbazide.

12. A composition according to claim 11 in which monoolefin polymer ispolyisobutylene.

13. A mineral lubricating oil containing a detergent quantity of aproduct obtained by reacting about one molecular proportion ofphosphorus pen'tasulfide with 2 to 5 molecular proportions ofpolyisobutylene having a molecular weight in the range of 100 to 50,000at a temperature of about 300 to about 550 F, and then reacting theproduct thus obtained with semicarbazide.

14. A mineral lubricating oil containing a detergent quantity of aproduct obtained by reacting about one molecular proportion ofphosphorus pentasulfide with 2 to 5 molecular proportions ofpolyisobutylene having a molecular weight in the range of 100 to 50,000at a temperature of about 300 to about 550 F., and then reacting theproduct thus obtained with thiosemicarbazide.

15. A composition consisting essentially of a mineral lubricating oiland 25 to 50% by weight based on the the total composition of a productobtained by preparing a I0 10 first reaction product chosen from thegroup consisting of (a) the products obtained by reacting a sulfide ofphosphorus with an essentially hydrocarbon material, (b) the productsobtained by reacting a mixture of the elements of phosphorus and sulfurwith an essentially hydrocarbon material and (c) the metal salts of (a)and (b), and then by reacting the said first reaction product with anorganic compound selected from the groups consisting of (d) compound ofthe composition,

wherein R1, Ra, R3, R4, and R5 are each selected from the groupsconsisting of hydrogen and hydrocarbon radicals containing 1 to 20carbon atoms each, and X is selected from the group consisting of oxygenand sulfur and (e) an inorganic acid salt of (d) provided that reactionproducts (a) and (b) are reacted only with compound (d) and reactionproduct (0) is reacted only with inorganic acid salt (2).

16. A composition consisting essentially of a mineral lubricating oiland to by weight based on the total composition of a product obtained byreacting phosphorus pentasulfide with a monoolefin polymer and reactingsuch reaction product with thiosemicarbazide.

No references cited.

1. A MINERAL OIL CONTAINING A DETERGENT QUANTITY OF A PRODUCT OBTAINEDBY PREPARING A FIRST REACTION PRODUCT CHOSEN FROM THE GROUP CONSISTINGOF (A) THE PRODUCTS OBTAINED BY REACTING A SULFIDE OF PHOSPHORUS WITH ANESSENTIALLY HYDROCARBON MATERIAL (B) THE PRODUCTS OBTAINED BY REACTING AMIXTURE OF THE ELEMENTS OF PHOSPHORUS AND SULFUR WITH AN ESSENTIALLYHYDROCARBON MATERIAL AND (C) THE METAL SALTS OF (A) AND (B), AND THEN BYREACTING THE SAID FIRST REACTION PRODUCT WITH AN ORGANIC COMPOUNDSELECTED FROM THE GROUP CONSISTING OF (D) COMPOUND OF THE COMPOSITION